Reactions of olefin derivatives in the presence of methathesis catalysts

ABSTRACT

The invention provides a method for synthesizing musk macrocycles comprising contacting an easily accessible diene starting materials bearing a Z-olefin moiety and performing a ring closing metathesis reaction in the presence of a Group 8 olefin metathesis catalyst.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/629,857, filed Feb. 13, 2018.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as avaluable synthetic method for the formation of carbon-carbon doublebonds. Recent advances in applications to organic syntheses and polymersyntheses mostly rely on developments of well-defined olefin metathesiscatalysts.

The technology of ruthenium metathesis catalysts has enabled thedevelopment of several research platforms including: ring openingmetathesis polymerization (ROMP), ring opening cross metathesis (ROCM),cross metathesis (CM), ring closing metathesis (RCM).

In another embodiment, the invention provides methods for the synthesisof macrocyclic compounds utilized in the fragrance industry.

The odor of musk is perhaps the most universally appreciated fragrance.The natural macrocyclic musk compounds turned out to be ketones (animalsources) and lactones (plant materials). They are 15- or 17-memberedring systems. The type of odor is influenced by the ring size. Startingfrom 14 ring atoms, a weak musk scent is perceived. Compounds with 15-16ring atoms exhibit strong musk odor.

Macrocyclic musk compounds are expected to be of increasing importancein the future, especially because many of them are naturally occurringand even the synthetic representatives closely resemble the naturalcounterparts. In addition, the progress in synthetic chemistrycontributes to declining prices and will stimulate increased use of thistype of musk compounds.

Synthetic musk compounds can be divided into three major classes:aromatic nitro musk compounds, polycyclic musk compounds, andmacrocyclic musk compounds. As such, macrocyclic musk compounds haveincreased in importance in recent years.

The synthesis of macrocyclic musk compounds is difficult, and, in manycases, it is a multi-step procedure. Due to the relatively highproduction costs, their economic importance is still limited. However,there is a constant demand for these musk compounds in bulk in perfumeryindustry.

There is a need for effective processes for preparing cyclic compoundsbased on medium and specifically based on large rings which have atleast one keto group. Medium rings generally have 8 to 11 carbon atoms,above 12 carbon atoms one talks of large rings, and compounds based onlarge rings are also referred to as macrocyclic compounds. Macrocyclicketones, lactones and epoxides as well as further functionalizedmacrocycles are aroma chemicals valued in the fragrance industry. Thereis a need to create new synthetic routes into the highly valued andvaluable macrocyclic musk compounds.

The present invention addresses the problems of the prior art andprovides an efficient and high-yielding synthesis of macrocyclic muskcompounds and their open-chain intermediates, utilizing cross metathesisreactions in the presence of Group 8 metal olefin metathesis catalysts.

The stereochemistry of the alkene, E or Z, in these cyclic structures isoften crucial to the biological activity of a molecule or its olfactorycharacteristics, and small amounts of impurity of the other stereoisomerin chemical mixtures can drastically decrease their potency. It isparticularly difficult to separate E- and Z-isomers as techniques fortheir separation are not general. As such, methods for producingstereochemically pure cyclic compounds are of paramount importance.

Controlling olefin stereochemistry in RCM reactions can be difficult.When using common non-selective metathesis catalysts, selectivity iscontrolled by the thermodynamic stability of the olefin products and canvary depending on ring size and double bond position.

Furthermore, high catalyst loadings are often needed formacrocyclization reactions using RCM. In these instances, removal ofresidual metals, the presence of which can be undesirable in the endproduct or could potentially isomerize products, can be difficult. Forsome applications, this requires further purification with additives orwith multiple chromatographic columns followed by treatment withcharcoal.

Common macrocyclic musk compounds include ambrettolide (9-ambrettolideand 7-ambrettolide), nirvanolide, habanolide, cosmone, muscenone,velvione, dihydrocivetone, exaltone, civetone and globanone.

The invention provides a method of forming macrocyclic musk compoundscomprising the steps of cross metathesizing a first olefin and a secondolefin in the presence of at least one Group 8 metal olefin metathesiscatalyst, to form a cross-metathesis product and then cyclizing thecross-metathesis product to form the desired macrocyclic musk compounds.

The macrocyclic musk compounds can be formed by ring closing metathesisof a diene, in the presence of at least one Group 8 metal olefinmetathesis catalyst. More particularly the invention is concerned withnovel methods for obtaining musk macrocycles in the Z configuration, viacross metathesis reactions, in the presence of at least one Group 8metal Z-stereoretentive olefin metathesis catalyst.

Using easily accessible diene starting materials bearing a Z-olefinmoiety, macrocyclization reactions generated products with significantlyhigher Z-selectivity in appreciably shorter reaction times, in higheryield, and with much lower catalyst loadings than in previously reportedsystems. Macrocyclic lactones ranging in size from twelve-membered toseventeen-membered rings are synthesized in moderate to high yields(68-79% yield) with excellent Z-selectivity (95%->99% Z).

SUMMARY OF THE INVENTION Musk Macrocycles

The present invention relates to a process, involving ring closingmetathesis in the presence of at least one Group 8 metal olefinmetathesis catalyst, for preparing cyclic compounds having at leasteight carbon atoms and at least one keto group, used in the fragranceindustry.

Ring closing metathesis reactions were achieved, using the catalysts ofthe invention and it was shown on a variety of substrates. Using astandard catalyst loading of 6 mol % often used in macrocyclizationreactions, reactions were completed within 1 h in dichloromethane understatic vacuum (30 mTorr) at 40° C. Twelve- to seventeen-membered ringswere all synthesized with high Z-selectivity (95-99% Z) in moderate tohigh yields (68-79% isolated yield). Yuzu lactone,(Z)-Oxacyclotridec-10-en-2-one, for example, is in high demand by theperfume industry and can be synthesized more rapidly and selectivelyusing ruthenium olefin metathesis catalysts than in previous reports.Larger macrocyclic lactones, fifteen-membered to seventeen-memberedrings, were synthesized in slightly higher yields than with smallertwelve- to fourteen-membered.

In summary, highly active, ruthenium-based olefin metathesis catalystswere used for generating highly Z-macrocycles (95-99% Z) from easilyavailable diene substrates with a Z-olefin moiety.

In another aspect, the macrocyclic musk compounds can be synthesized viaring closing olefin metathesis reactions of bis-olefins in the presenceof at least one Group 8 metal olefin metathesis catalyst.

In another embodiment, the ring-closing metathesis reaction product hasa carbon-carbon double bond in a Z-configuration and is represented bythe structure of Formula (A):

wherein:q is 1, 2, 3, or 4; andp is 4, 5, 6, or 7.

In another embodiment, the ring-closing metathesis reaction product hasa carbon-carbon double bond in a Z-configuration and is represented bythe structure of Formula (B):

wherein:r is 1, 2, 3, or 4; andv is 4, 5, 6, or 7.

In another embodiment, the ring-closing metathesis reaction product hasa carbon-carbon double bond in a Z-configuration and is represented bythe structure of Formula (C):

wherein:q^(c) is 1, 2, 3, or 4; andp^(c) is 4, 5, 6, or 7.

In another embodiment, the ring-closing metathesis reaction product hasa carbon-carbon double bond and is represented by the structure ofFormula (K):

wherein:x is 2, 3, 4 or 5;y is 5, 6, 7, or 8.

In another aspect the invention provides a method of forming amacrocyclic musk compound comprising the steps of cross metathesizing afirst olefin and a second olefin in the presence of at least one Group 8metal olefin metathesis catalyst, to form an intermediate of said firstand second olefin and cyclizing the intermediate to form the macrocyclicmusk compound.

These and other aspects of the present invention will be apparent to oneof skill in the art, in light of the following detailed description andexamples. Furthermore, it is to be understood that none of theembodiments or examples of the invention described herein are to beinterpreted as being limiting.

DETAILED DESCRIPTION

Unless otherwise indicated, the invention is not limited to specificreactants, substituents, catalysts, reaction conditions, or the like, assuch may vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an olefin” includesa single olefin as well as a combination or mixture of two or moreolefins, reference to “a substituent” encompasses a single substituentas well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “forexample”, “for instance”, “such as”, or “including” are meant tointroduce examples that further clarify more general subject matter.Unless otherwise specified, these examples are provided only as an aidfor understanding the invention and are not meant to be limiting in anyfashion.

In this specification and in the claims, that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to 30 carbon atoms, generally containing 1 to 24 carbonatoms, typically 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, aswell as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms,and the specific term “cycloalkyl” intends a cyclic alkyl group,typically having 3 to 12, or 4 to 12, or 3 to 10, or 3 to 8, carbonatoms. The term “substituted alkyl” refers to alkyl substituted with oneor more substituent groups, and the terms “heteroatom-containing alkyl”and “heteroalkyl” refer to alkyl in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkyl” and “lower alkyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing alkyl and loweralkyl, respectively.

The term “alkylene” as used herein refers to a divalent linear,branched, or cyclic alkyl group, where “alkyl” is as defined herein.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to 30 carbon atoms containing at least onedouble bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl,iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl,tetracosenyl, and the like. Generally, “alkenyl” groups herein contain 2to 24 carbon atoms, typically “alkenyl” groups herein contain 2 to 12carbon atoms. The term “lower alkenyl” intends an “alkenyl” group of 2to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic“alkenyl” group, typically having 5 to 8 carbon atoms. The term“substituted alkenyl” refers to “alkenyl” substituted with one or moresubstituent groups, and the terms “heteroatom-containing alkenyl” and“heteroalkenyl” refer to “alkenyl” in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkenyl” and “lower alkenyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing “alkenyl” andlower “alkenyl”, respectively. The term “alkenyl” is usedinterchangeably with the term “olefin” herein.

The term “alkenylene” as used herein refers to a divalent linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined herein.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to 30 carbon atoms containing at least one triplebond, such as ethynyl, n-propynyl, and the like. Generally, “alkynyl”groups herein contain 2 to 24 carbon atoms; typical “alkynyl” groupsdescribed herein contain 2 to 12 carbon atoms. The term “lower alkynyl”intends an “alkynyl” group of 2 to 6 carbon atoms. The term “substitutedalkynyl” refers to “alkynyl” substituted with one or more substituentgroups, and the terms “heteroatom-containing alkynyl” and“heteroalkynyl” refer to “alkynyl” in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkynyl” and “lower alkynyl” include linear, branched, unsubstituted,substituted, and/or heteroatom-containing “alkynyl” and lower “alkynyl”respectively.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group can berepresented as —O-alkyl where alkyl is as defined herein. A “loweralkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer toan alkenyl and lower alkenyl group bound through a single, terminalether linkage, and “alkynyloxy” and “lower alkynyloxy” respectivelyrefer to an alkynyl and lower alkynyl group bound through a single,terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, directly linked, or indirectlylinked (such that the different aromatic rings are bound to a commongroup such as a methylene or ethylene moiety). “Aryl” groups contain 5to 30 carbon atoms, generally “aryl” groups contain 5 to 20 carbonatoms; and typically, “aryl” groups contain 5 to 14 carbon atoms.Exemplary “aryl” groups contain one aromatic ring or two fused or linkedaromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether,diphenylamine, benzophenone, and the like. “Substituted aryl” refers toan aryl moiety substituted with one or more substituent groups; forexample, 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl,2,6-di-iso-propylphenyl (i.e., DIPP or DiPP), 2-isopropyl-phenyl (i.e.,IPP, Ipp or ipp), 2-iso-propyl-6-methylphenyl (i.e., MIPP or Mipp orMiPP). The terms “heteroatom-containing aryl” and “heteroaryl” refer to“aryl” substituents in which at least one carbon atom is replaced with aheteroatom, as will be described in further detail infra.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined herein.An “aryloxy” group can be represented as —O-aryl where aryl is asdefined herein. Preferred “aryloxy” groups contain 5 to 24 carbon atoms,and particularly preferred “aryloxy” groups contain 5 to 14 carbonatoms. Examples of “aryloxy” groups include, without limitation,phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy,o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy,2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined herein. “Alkaryl”and “aralkyl” groups contain 6 to 30 carbon atoms; generally, “alkaryl”and “aralkyl” groups contain 6 to 20 carbon atoms; and typically,“alkaryl” and “aralkyl” groups contain 6 to 16 carbon atoms. “Alkaryl”groups include, for example, p-methylphenyl, 2,4-dimethylphenyl,p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl,3-ethyl-cyclopenta-1,4-diene, and the like. Examples of “aralkyl” groupsinclude, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl,4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl,4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. Theterms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula—OR wherein R is “alkaryl” or “aralkyl”, respectively, as definedherein.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers tosubstituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or—O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as definedherein.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom containing, and that canbe monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used inthe conventional sense to refer to an aliphatic cyclic moiety, asopposed to an aromatic cyclic moiety, and can be monocyclic, bicyclic,or polycyclic.

The terms “halo”, “halogen” and “halide” are used in the conventionalsense to refer to a chloro, bromo, fluoro, or iodo substituent.

The term “hydrocarbyl” refers to univalent “hydrocarbyl” moietiescontaining 1 to 30 carbon atoms, typically containing 1 to 24 carbonatoms, specifically containing 1 to 12 carbon atoms, including linear,branched, cyclic, saturated, and unsaturated species, such as alkylgroups, alkenyl groups, aryl groups, and the like. The term “lowerhydrocarbyl” intends a “hydrocarbyl” group of 1 to 6 carbon atoms,typically 1 to 4 carbon atoms, and the term “hydrocarbylene” intends adivalent “hydrocarbyl” moiety containing 1 to 30 carbon atoms, typically1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, includinglinear, branched, cyclic, saturated and unsaturated species. The term“lower hydrocarbylene” intends a “hydrocarbylene” group of 1 to 6 carbonatoms. “Substituted hydrocarbyl” refers to “hydrocarbyl” substitutedwith one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom. Similarly, “substituted hydrocarbylene” refers to“hydrocarbylene” substituted with one or more substituent groups, andthe terms “heteroatom-containing hydrocarbylene” andheterohydrocarbylene” refer to “hydrocarbylene” in which at least onecarbon atom is replaced with a heteroatom. Unless otherwise indicated,the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted asincluding substituted and/or heteroatom-containing “hydrocarbyl” and“hydrocarbylene” moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” andheteroaromatic” respectively refer to “aryl” and “aromatic” substituentsthat are heteroatom-containing, and the like. It should be noted that a“heterocyclic” group or compound may or may not be aromatic, and furtherthat “heterocycles” can be monocyclic, bicyclic, or polycyclic asdescribed herein with respect to the term “aryl.” Examples ofheteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl,N-alkylated amino alkyl, and the like. Examples of heteroarylsubstituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl,indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (orother) atom is replaced with one or more non-hydrogen substituents.Examples of such substituents include, without limitation: functionalgroups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—(CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxyl (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CS)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CS)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CS)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CS)—N(C₅-C₂₄ aryl)₂), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl (—(CS)—H),amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino, di-(C₁-C₂₄alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino,di-(C₅-C₂₄ aryl)-substituted amino, (C₁-C₂₄ alkyl)(C₅-C₂₄aryl)-substituted amino, (C₂-C₂₄ alkyl)-amido (—NH—(CO)-alkyl), (C₆-C₂₄aryl)-amido (—NH—(CO)-aryl), imino (—CR═NH where R is hydrogen, C₁-C₂₄alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), (C₂-C₂₀alkyl)-imino (—CR═N(alkyl), where R is hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl),where R is hydrogen, C₁-C₂ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O—), (C₁-C₂₄ alkyl)-sulfanyl (—S-alkyl; also termed “alkylthio”),(C₅-C₂₄ aryl)-sulfanyl (—S-aryl; also termed “arylthio”), (C₁-C₂₄alkyl)-sulfinyl (—(SO)-alkyl), (C₅-C₂₄ aryl)-sulfinyl (—(SO)-aryl),(C₁-C₂₄ alkyl)-sulfonyl (—SO₂-alkyl), mono-(C₁-C₂₄ alkyl)-aminosulfonyl—SO₂—N(H)alkyl), di-(C₁-C₂₄ alkyl)-aminosulfonyl —SO₂—N(alkyl)₂, (C₅-C₂₄aryl)-sulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂),phosphonato (—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), andphosphino (—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferablyC₁-C₁₂ alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferablyC₂-C₁₂ alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl(preferably C₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl(preferably C₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl),and C₆-C₂₄ aralkyl (preferably C₆-C₁₆ aralkyl).

The term “NHC” ligand, refers to a N-heterocyclic carbene ligand.

The term “CAAC” ligand, refers to a cyclic alkyl amino carbene ligandalso known as “Bertrand-type ligand”.

Functional groups, such as ether, ester, hydroxyl, carbonate, may beprotected in cases where the functional group interferes with the olefinmetathesis catalyst, and any of the protecting groups commonly used inthe art may be employed. Acceptable protecting groups may be found, forexample, in Greene et al., Protective Groups in Organic Synthesis, 4rdEd. (Published by John Wiley & Sons, Inc., Hoboken, N.J. 2007).

The geometry of the olefins described in this patent application may beof E-configuration, or of Z-configuration, or of a mixture of E- andZ-configurations. Applicants have represented a mixture of double-bondisomers by using a squiggly bond “

”. For example, as represented herein, structure

exemplifies either the E-configuration

or the Z-configuration

or can represent a mixture of E- and Z-configurations. Suitable etherprotecting groups include a branched or non-branched alkyl moietycontaining 1 to 5 carbon atoms, for example methyl, ethyl, propyl,i-propyl, t-Bu or t-amyl.

Suitable ester protecting groups include —C(O)R, wherein R=hydrogen, ora branched or non-branched alkyl moiety containing 1 to 7 carbon atoms,for example methyl, ethyl, propyl, i-propyl, t-butyl or t-amyl.

Suitable silyl ether protecting groups include —Si(R)₃; wherein R is abranched or unbranched alkyl moiety, which may include methyl, ethyl andpropyl and t-butyl.

Suitable carbonate protecting groups include —C(O)OR, wherein R is abranched or non-branched alkyl moiety, for example methyl, ethyl orpropyl.

By “sulfoxide group” is meant —[S(O)]—.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, orother moiety, at least one hydrogen atom bound to a carbon (or other)atom is replaced with one or more functional groups such as thosedescribed herein. The term “functional group” is meant to include anyfunctional species that is suitable for the uses described herein. Inparticular, as used herein, a functional group would necessarily possessthe ability to react with or bond to corresponding functional groups ona substrate surface.

In addition, the functional groups may, if a particular group permits,be further substituted with one or more additional functional groups orwith one or more hydrocarbyl moieties such as those specificallyenumerated herein. Analogously, the herein-mentioned hydrocarbylmoieties can be further substituted with one or more functional groupsor additional hydrocarbyl moieties such as those specificallyenumerated.

“Optional” or “optionally” means that the subsequently describedcircumstance can or cannot occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent can or cannot be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

Group 8 Metal Olefin Metathesis Catalyst

The Group 8 metal olefin metathesis catalysts of the invention arerepresented by the general structure of Formula (1)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group [—S(O)—];

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically, X¹ and X² are independently Cl, Br, I or F; and

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene.

In some embodiments of Formula (1),

wherein:

M, X¹ and X² are as defined herein;

X³ and X⁴ are independently O or S; and

R^(x), R^(y), R^(w) and R^(z) are independently hydrogen, halogen,unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; or R^(x) and R^(y) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(w) and R^(z) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(y) and R^(w) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl.

The Group 8 metal olefin metathesis catalysts used in the invention canbe represented by the structure of Formula (2):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L¹ and L² are independently a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene;

X³ and X⁴ are independently O or S; typically, X³ and X⁴ areindependently S; and

R^(x), R^(y), R^(w) and R^(z) are independently hydrogen, halogen,unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally R^(x), R^(y), R^(w) and R^(z) are independentlyhydrogen, halogen, unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(x),R^(y), R^(w) and R^(z) are independently C₁-C₆ alkyl, hydrogen,unsubstituted phenyl, substituted phenyl or halogen; or R^(x) and R^(y)are linked together to form an unsubstituted bicyclic or polycyclic arylor a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) arelinked together to form an unsubstituted bicyclic or polycyclic aryl ora substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl.

The Group 8 metal olefin metathesis catalysts used in the invention arerepresented by the structure of Formula (3),

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically, X¹ and X² are independently Cl, Br, I or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene;

X⁵ and Y⁵ are independently C, CR^(3A), N, O, S, or P; only one of X⁵ orY⁵ can be C or CR^(3A); typically, X⁵ and Y⁵ are independently N;

Q¹, Q², R³, R^(3A) and R⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, Q¹, Q², R³, R^(3A) and R⁴ are optionally linkedto X⁵ or Y⁵ via a linker such as unsubstituted hydrocarbylene,substituted hydrocarbylene, unsubstituted heteroatom-containinghydrocarbylene, substituted heteroatom-containing hydrocarbylene, or—(CO)—; typically Q¹, Q², R³, R^(3A) and R⁴ are directly linked to X⁵ orY⁵; and

p is 0 when X⁵ is O or S, p is 1 when X⁵ is N, P or CR^(3A), and p is 2when X⁵ is C; q is 0 when Y⁵ is O or S, q is 1 when Y⁵ is N, P orCR^(3A), and q is 2 when X⁵ is C.

The Group 8 metal olefin metathesis catalysts used in the invention arerepresented by the structure of Formula (4):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

or R^(a) and R^(b) are linked together to form a five or asix-heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically, X¹ and X² are independently Cl, Br, I or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene;

X⁵ and Y⁵ are independently C, CR^(3A), or N; only one of X⁵ or Y5 canbe C or CR^(3A); typically, X⁵ and Y⁵ are independently N;

R^(3A) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; Q is a linker, typicallyunsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstitutedheteroatom-containing hydrocarbylene, or substitutedheteroatom-containing hydrocarbylene; generally Q is a two-atom linkagehaving the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or —[CR¹¹═CR¹³]—;typically Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—, wherein R, R¹², R¹³, andR¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically R¹¹, R¹², R¹³and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substitutedC₁-C₁₂ heteroalkyl, unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄aryl;

“s” and “t” are independently 1 or 2; typically, “s” and “t” areindependently 1; or any two of R, R¹², R¹³, and R¹⁴ are optionallylinked together to form a substituted or unsubstituted, saturated orunsaturated ring structure;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryland halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl or2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryland halide; typically, R⁴ is, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl or2-methyl-phenyl; or when X⁵ is CR^(3A), then R^(3A) and R⁴ can fromtogether a five to ten membered cycloalkyl or heterocyclic ring, withthe carbon atom to which they are attached.

In some embodiments of Formula (4),

wherein: X¹, X², X³, X⁴, M, R^(x), R^(y), R^(w) and R^(z) are as definedherein.

When Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t), s is 1, t is 1 and R¹¹, R¹²,R¹³, and R¹⁴ are independently hydrogen, and M is ruthenium, then olefinmetathesis catalyst of Formula (4), is represented by the structure ofFormula (5)

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedhetero atom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl,C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked togetherto form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group; typically, R^(a) and R^(b) are linked together to forma tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; generally, X¹ and X² are independently Cl, Br, I or F;typically, X¹ and X² are independently Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (5) are described in Table (1), wherein X¹ is Cland X² is Cl.

TABLE (1) Olefin Metathesis Catalysts of Formula (5) Catalyst R¹ R² R³R⁴ R^(a) R^(b) 1 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 2 H Ph Mes Mes Me Me 3 HPh Mipp Mipp Me Me 4 H Ph adamantyl Mes Me Me 5 H Ph DIPP DIPP Me Me 6 HPh IPP IPP Me Me 7 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 8 H

Mes Mes Me Me 9 H

Mipp Mipp Me Me 10 H

adamantyl Mes Me Me 11 H

DIPP DIPP Me Me 12 H

IPP IPP Me Me 13 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 14 H

Mes Mes Me Me 15 H

Mipp Mipp Me Me 16 H

adamantyl Me Me Me 17 H

DIPP DIPP Me Me 18 H

IPP IPP Me Me 19

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 20

Mes Mes Me Me 21

Mipp Mipp Me Me 22

adamantyl Mes Me Me 23

DIPP DIPP Me Me 24

IPP IPP Me Me 25 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

26 H Ph Mes Mes

27 H Ph Mipp Mipp

28 H Ph adamantyl Mes

29 H Ph DIPP DIPP

30 H Ph IPP IPP

31 H

2-Me—C₆H₅ 2-Me—C₆H₅

32 H

Mes Mes

33 H

Mipp Mipp

34 H

adamantyl Mes

35 H

DIPP DIPP

36 H

IPP IPP

37 H

2-Me—C₆H₅ 2-Me—C₆H₅

38 H

Mes Mes

39 H

Mipp Mipp

40 H

adamantyl Mes

41 H

DIPP DIPP

42 H

IPP IPP

43

2-Me—C₆H₅ 2-Me—C₆H

44

Mes Mes

45

Mipp Mipp

46

adamantyl Mes

47

DIPP DIPP

48

IPP IPP

49 H Ph 2-Me—C₆H 2-Me—C₆H n-Bu n-Bu 50 H Ph Mes Mes n-Bu n-Bu 51 H PhMipp Mipp n-Bu n-Bu 52 H Ph adamantyl Mes n-Bu n-Bu 53 H Ph DIPP DIPPn-Bu n-Bu 54 H Ph IPP IPP n-Bu n-Bu 55 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 56 H

Mes Mes n-Bu n-Bu 57 H

Mipp Mipp n-Bu n-Bu 58 H

adamantyl Mes n-Bu n-Bu 59 H

DIPP DIPP n-Bu n-Bu 60 H

IPP IPP n-Bu n-Bu 61 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 62 H

Mes Mes n-Bu n-Bu 63 H

Mipp Mipp n-Bu n-Bu 64 H

adamantyl Mes n-Bu n-Bu 65 H

DIPP DIPP n-Bu n-Bu 66 H

IPP IPP n-Bu n-Bu 67

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 68

Mes Mes n-Bu n-Bu 69

Mipp Mipp n-Bu n-Bu 70

adamantyl Mes n-Bu n-Bu 71

DIPP DIPP n-Bu n-Bu 72

IPP IPP n-Bu n-Buwherein: Mes is

Mipp is

DIPP is

adamantyl is

IPP is

2-Me-C₆H₅ is

Me is CH₃—, n-Bu is [CH₃—(CH₂)₃—], Ph is

and

is [—(CH₂)₄—].

When Q is a two-atom linkage having the structure —[CR¹¹═CR¹³]— and R¹¹and R¹³ are hydrogen, and M is ruthenium, then the olefin metathesiscatalyst of Formula (4), is represented by the structure of Formula (6)

wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl orsubstituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; R^(a) is unsubstituted C₁-C₁₀ alkyl,substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substitutedC₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; R^(b) is unsubstituted C₁-C₁₀ alkyl,substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substitutedC₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl;or R^(a) and R^(b) are linked together to form a five or asix-heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; X¹ and X² are independently Cl, Br, I or F; typically, X¹and X² are independently Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₁-C₁₀ cycloalkyl,substituted C₁-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (6) are described in Table (2), wherein X¹ is Cland X² is Cl.

TABLE (2) Olefin Metathesis Catalysts of Formula (6) Catalyst R¹ R² R³R⁴ R^(a) R^(b) 73 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 74 H Ph Mes Mes Me Me75 H Ph Mipp Mipp Me Me 76 H Ph adamantyl Mes Me Me 77 H Ph DIPP DIPP MeMe 78 H Ph IPP IPP Me Me 79 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 80 H

Mes Mes Me Me 81 H

Mipp Mipp Me Me 82 H

adamantyl Mes Me Me 83 H

DIPP DIPP Me Me 84 H

IPP IPP Me Me 85 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 86 H

Mes Mes Me Me 87 H

Mipp Mipp Me Me 88 H

adamantyl Mes Me Me 89 H

DIPP DIPP Me Me 90 H

IPP IPP Me Me 91

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 92

Mes Mes Me Me 93

Mipp Mipp Me Me 94

adamantyl Mes Me Me 95

DIPP DIPP Me Me 96

IPP IPP Me Me 97 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

98 H Ph Mes Mes

99 H Ph Mipp Mipp

100 H Ph adamantyl Mes

101 H Ph DIPP DIPP

102 H Ph IPP IPP

103 H

2-Me—C₆H₅ 2-Me—C₆H₅

104 H

Mes Mes

105 H

Mipp Mipp

106 H

adamantyl Mes

107 H

DIPP DIPP

108 H

IPP IPP

109 H

2-Me—C₆H₅ 2-Me—C₆H₅

110 H

Mes Mes

111 H

Mipp Mipp

112 H

adamantyl Mes

113 H

DIPP DIPP

114 H

IPP IPP

115

2-Me—C₆H₅ 2-Me—C₆H₅

116

Mes Mes

117

Mipp Mipp

118

adamantyl Mes

119

DIPP DIPP

120

IPP IPP

121 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 122 H Ph Mes Mes n-Bu n-Bu 123 HPh Mipp Mipp n-Bu n-Bu 124 H Ph adamantyl Mes n-Bu n-Bu 125 H Ph DIPPDIPP n-Bu n-Bu 126 H Ph IPP IPP n-Bu n-Bu 127 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 128 H

Mes Mes n-Bu n-Bu 129 H

Mipp Mipp n-Bu n-Bu 130 H

adamantyl Mes n-Bu n-Bu 131 H

DIPP DIPP n-Bu n-Bu 132 H

IPP IPP n-Bu n-Bu 133 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 134 H

Mes Mes n-Bu n-Bu 135 H

Mipp Mipp n-Bu n-Bu 136 H

adamantyl Mes n-Bu n-Bu 137 H

DIPP DIPP n-Bu n-Bu 138 H

IPP IPP n-Bu n-Bu 139

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 140

Mes Mes n-Bu n-Bu 141

Mipp Mipp n-Bu n-Bu 142

adamantyl Mes n-Bu n-Bu 143

DIPP DIPP n-Bu n-Bu 144

IPP IPP n-Bu n-Bu

When, Y is N and X⁵ is CR^(3A) and M is ruthenium then, the olefinmetathesis catalyst of Formula (4), is represented by the structure ofFormula (7)

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked togetherto form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁ alkyl, unsubstituted C₃-C₁ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl or phenyl; or R and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; generally, X¹ and X² are independently Cl, Br, I or F;typically, X¹ and X² are independently Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl or 2-methyl-phenyl;

R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R¹¹, R¹², R¹³ and R¹⁴ are independentlyhydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl,unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl,unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl,substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl orsubstituted C₆-C₂₄ heteroaralkyl; typically, R¹¹ and R¹² areindependently methyl and R¹³ and R¹⁴ are independently hydrogen;

R^(3A) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(3A) is unsubstitutedC₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl,substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substitutedC₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl,unsubstituted C₆-C₂₄ heteroaralkyl or substituted C₆-C₂₄ heteroaralkyl;typically R^(3A) is methyl, ethyl, n-propyl, or phenyl; or R^(3A)together with R⁴ can form a five to ten membered cycloalkyl orheterocyclic ring, with the carbon atom to which they are attached; and

R⁴ is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl,substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substitutedC₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl,unsubstituted C₆-C₂₄ heteroaralkyl or substituted C₆-C₂₄ heteroaralkyl;typically R⁴ is methyl, ethyl, n-propyl, or phenyl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (7) are described in Table (3), wherein X¹ is Cl,X² is Cl, R¹¹ is methyl, R¹² is methyl, R¹³ is hydrogen and R¹⁴ ishydrogen.

TABLE (3) Olefin Metathesis Catalysts of Formula (7) Catalyst R¹ R²R^(a) R^(b) R³ R^(3A) R⁴ 145 H Ph Me Me 2-Me—C₆H₅ Me Me 146 H Ph Me MeMes Me Me 147 H Ph Me Me Mipp Me Me 148 H Ph Me Me EMP Me Me 149 H Ph MeMe DIPP Me Me 150 H Ph Me Me IPP Me Me 151 H

Me Me 2-Me—C₆H₅ Me Me 152 H

Me Me Mes Me Me 153 H

Me Me Mipp Me Me 154 H

Me Me EMP Me Me 155 H

Me Me DIPP Me Me 156 H

Me Me IPP Me Me 157 H

Me Me 2-Me—C₆H₅ Me Me 158 H

Me Me Mes Me Me 159 H

Me Me Mipp Me Me 160 H

Me Me EMP Me Me 161 H

Me Me DIPP Me Me 162 H

Me Me IPP Me Me 163

Me Me 2-Me—C₆H₅ Me Me 164

Me Me Mes Me Me 165

Me Me Mipp Me Me 166

Me Me EMP Me Me 167

Me Me DIPP Me Me 168

Me Me IPP Me Me 169 H Ph

2-Me—C₆H₅ Me Me 170 H Ph

Mes Me Me 171 H Ph

Mipp Me Me 172 H Ph

EMP Me Me 173 H Ph

DIPP Me Me 174 H Ph

IPP Me Me 175 H

2-Me—C₆H₅ Me Me 176 H

Mes Me Me 177 H

Mipp Me Me 178 H

EMP Me Me 179 H

DIPP Me Me 180 H

IPP Me Me 181 H

2-Me—C₆H₅ Me Me 182 H

Mes Me Me 183 H

Mipp Me Me 184 H

EMP Me Me 185 H

DIPP Me Me 186 H

IPP Me Me 187

2-Me—C6H5 Me Me 188

Mes Me Me 189

Mipp Me Me 190

EMP Me Me 191

DIPP Me Me 192

IPP Me Me 193 H Ph n-Bu n-Bu 2-Me—C₆H₅ Me Me 194 H Ph n-Bu n-Bu Mes MeMe 195 H Ph n-Bu n-Bu Mipp Me Me 196 H Ph n-Bu n-Bu EMP Me Me 197 H Phn-Bu n-Bu DIPP Me Me 198 H Ph n-Bu n-Bu IPP Me Me 199 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 200 H

n-Bu n-Bu Mes Me Me 201 H

n-Bu n-Bu Mipp Me Me 202 H

n-Bu n-Bu EMP Me Me 203 H

n-Bu n-Bu DIPP Me Me 204 H

n-Bu n-Bu IPP Me Me 205 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 206 H

n-Bu n-Bu Mes Me Me 207 H

n-Bu n-Bu Mipp Me Me 208 H

n-Bu n-Bu EMP Me Me 209 H

n-Bu n-Bu DIPP Me Me 210 H

n-Bu n-Bu IPP Me Me 211

n-Bu n-Bu 2-Me—C₆H₅ Me Me 212

n-Bu n-Bu Mes Me Me 213

n-Bu n-Bu Mipp Me Me 214

n-Bu n-Bu EMP Me Me 215

n-Bu n-Bu DIPP Me Me 216

n-Bu n-Bu IPP Me Mewherein EMP is

When, L¹ is a CAAC ligand of formula:

m is 0, and M is ruthenium then, the olefin metathesis catalyst ofFormula (1), is represented by the structure of Formula (7A)

wherein X¹, X², R¹, R², R^(a) and R^(b) are as defined herein;

X is —CR^(1a)R^(2a)—;

a is 1 or 2;

R^(1a) is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl,optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)XR²⁵,—P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with R^(2a) forms anoptionally substituted spiro monocyclic or spiro polycyclicC₃₋₁₀cycloalkyl or spiro heterocyclic ring, with the carbon atom towhich they are attached, or together with R³ or together with R⁴ formsan optionally substituted polycyclic ring;

R^(2a) is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl,optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵,—P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with Ria forms a spiromonocyclic or spiro polycyclic C₃₋₁₀cycloalkyl or spiro heterocyclicring, with the carbon atom to which they are attached, or together withR³ or together with R⁴ forms an optionally substituted polycyclic ring;

Y is —CR^(1b)R^(2b)—;

b is 0, 1 or 2;

R^(1b) is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl,optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵,—P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with R^(2b) forms a five-,six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbonatom to which they are attached;

R^(2b) is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl,optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)XR²⁵,P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with R^(1b) forms a five-,six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbonatom to which they are attached;

R^(3a) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹,—OR²², CN, —NR²³R²⁴ NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂,—SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R^(1a) or together with R^(2a) canform an optionally substituted polycyclic ring, or together with R^(3a)can form an optionally substituted spiro monocyclic or spiro polycyclicC₃₋₁₀ cycloalkyl;

R^(3b) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹,—OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂,—SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R^(1a) or together with R^(2a) canform an optionally substituted polycyclic ring, or together with R³ canform an optionally substituted spiro monocyclic or spiro polycyclicC₃₋₁₀ cycloalkyl;

R^(4a) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹,—OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂,—SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with Ria or together with R^(2a) can forman optionally substituted polycyclic ring, or together with R^(4a) canform an optionally substituted spiro monocyclic or spiro polycyclicC₃₋₁₀ cycloalkyl;

R^(4b) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹,—OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂,—SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R^(1a) or together with R^(2a) canform an optionally substituted polycyclic ring, or together with R⁴ canform an optionally substituted spiro monocyclic or spiro polycyclicC₃₋₁₀ cycloalkyl;

R⁵ is H, optionally substituted C₁₋₂₄ alkyl, halogen-C(O)R²¹, —OR²², CN,—NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R², —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷,optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R⁶ can form an optionallysubstituted polycyclic ring;

R⁶ is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²²,CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷,optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R⁵ or together with R⁷ can form anoptionally substituted polycyclic ring;

R⁷ is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²²,CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷,optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R⁶ or together with R⁸ can form anoptionally substituted polycyclic ring;

R⁸ is H, optionally substituted C₁₋₂₄ alkyl, halogen-C(O)R²¹, —OR²², CN,—NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷,optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R⁷ or together with R⁹ can form anoptionally substituted polycyclic ring;

R⁹ is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²²,CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷,optionally substituted heterocycle, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl, or together with R⁸ can form a polycyclic ring;

R²¹ is OH, OR²⁶, NR²³R²⁴, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;

R²² is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²³ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²⁴ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²⁵ is H, optionally substituted C₁₋₂₄ alkyl, OR²², —NR²³R²⁴, optionallysubstituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;

R²⁶ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R² is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

x is 1 or 2; and with the provisos

a. when a is 2, then the “X-X” bond can be saturated or unsaturated;b. when b is 2, the “Y-Y” bond can be saturated or unsaturated;c. when a is 2, and the “X-X” bond is unsaturated, then R^(2a) is nil;d. when b is 1, then R^(3a) and R^(4a) are both nil;e. when b is 2, then R^(3a) and R^(4a) are both nil; andf. when b is 2, and the “Y-Y” bond is unsaturated, then R^(2b) is nil.

Depending on the values of a, b, X and Y, Moiety (A) of the CAAC ligand

is represented by structures selected from Table (4).

TABLE 4 Structures of Moiety (A) of the CAAC ligands

(A1)

(A2)

(A3)

(A4)

(A5)

(A6)

(A7)

(A8)

(A9)

(A10)

(A11)

(A12)

(A13)wherein: R¹, R², R^(a), R^(b), R^(3a), R^(3b), R^(4a), R^(4b), R⁵, R⁶,R⁷, R⁸ R⁹, R^(1a), R^(1b), X¹, X², X, and Y are as defined herein.

The nomenclature of the structures of Formula (7A) is determined by theMoiety (A) structures selected from Table (4). For example, thestructure below is assigned Formula (7A2), since Moiety (A2) is presentin the CAAC ligand.

TABLE 5 Olefin Metathesis Catalysts of Formula (7A)

Formula (7A10)

Formula (7A13)

Formula (7A12)

Formula (7A6)

Formula (7A11)

Formula (7A8)

Formula (7A9)

Formula (7A7)

Formula (7A5)

Formula (7A4)

Formula (7A3)

Formula (7A1)wherein: R¹, R², R^(a), R^(b) R^(3a), R^(3b), R^(4a), R^(4b), R⁵, R⁶,R⁷, R⁸ R⁹, R^(1a), R^(1b), X¹, X², X, and Y are as defined herein.

When, L¹ is a N-heterocyclic carbene ligand represented by

and X³ and X⁴ are independently S, and M is ruthenium then, the olefinmetathesis catalyst of Formula (2), is represented by the structure ofFormula (8)

wherein:

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a)is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexylor phenyl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(b)is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexylor phenyl; or R^(a) and R^(b) are linked together to form a five or asix-heterocyclic membered ring with the sulfoxide group;

R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to threesubstituents selected from unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R³ isadamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl or 2-methyl-phenyl;

R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to threesubstituents selected from unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl or 2-methyl-phenyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆alkyl or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene;

R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl, or hydrogen;generally, R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ ishydrogen and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ areindependently hydrogen; and

R^(x), R^(y), R^(w) and R^(z) are independently C₁-C₆ alkyl, hydrogen,halogen, unsubstituted phenyl or substituted phenyl; generally R^(x) ismethyl, hydrogen or Cl, R^(y) is hydrogen, R^(w) is hydrogen, R^(z) isCl, t-butyl, hydrogen or phenyl; or R^(x) and R^(y) are linked togetherto form an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (8) are described in Table (6), wherein R^(a) ismethyl, R^(b) is methyl, R¹¹ is hydrogen, R¹² is hydrogen, R¹³ ishydrogen, R¹⁴ is hydrogen, R^(y) is hydrogen and R^(w) is hydrogen.

TABLE 6 Olefin Metathesis Catalysts of Formula (8) Cata- lyst R¹ R² R³R⁴ R^(x) R^(z) 217 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 218 H Ph Mes Mes Cl Cl219 H Ph Mipp Mipp Cl Cl 220 H Ph DIPP DIPP Cl Cl 221 H Ph IPP IPP Cl Cl222 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 223 H

Mes Mes Cl Cl 224 H

Mipp Mipp Cl Cl 225 H

DIPP DIPP Cl Cl 226 H

IPP IPP Cl Cl 227 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 228 H

Mes Mes Cl Cl 229 H

Mipp Mipp Cl Cl 230 H

DIPP DIPP Cl Cl 231 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 232 H

Mes Mes Cl Cl 233 H

Mipp Mipp Cl Cl 234 H

DIPP DIPP Cl Cl 235 H

IPP IPP Cl Cl 236 H

IPP IPP Cl Cl 237

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 238

Mes Mes Cl Cl 239

Mipp Me Cl Cl 240

DIPP DIPP Cl Cl 241

IPP Me Cl Cl 242 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 243 H Ph Mes Mes H Ph 244H Ph Mipp Mipp H Ph 245 H Ph DIPP DIPP H Ph 246 H Ph IPP IPP H Ph 247 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 248 H

Mes Mes H Ph 249 H

Mipp Mipp H Ph 250 H

DIPP DIPP H Ph 251 H

IPP IPP H Ph 252 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 253 H

Mes Mes H Ph 254 H

Mipp Mipp H Ph 255 H

DIPP DIPP H Ph 256 H

IPP IPP H Ph 257

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 258

Mes Mes H Ph 259

Mipp Mipp H Ph 260

DIPP DIPP H Ph 261

IPP IPP H Ph 262 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 263 H Ph Mes Mes Met-Bu 264 H Ph Mipp Mipp Me t-Bu 265 H Ph DIPP DIPP Me t-Bu 266 H Ph IPPIPP Me t-Bu 267 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 268 H

Mes Mes Me t-Bu 269 H

Mipp Mipp Me t-Bu 270 H

DIPP DIPP Me t-Bu 271 H

IPP IPP Me t-Bu 272 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 273 H

Mes Mes Me t-Bu 274 H

Mipp Mipp Me t-Bu 275 H

DIPP DIPP Me t-Bu 276 H

IPP IPP Me t-Bu 277

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 278

Mes Mes Me t-Bu 279

Mipp Mipp Me t-Bu 280

DIPP DIPP Me t-Bu 281

IPP IPP Me t-Bu

Non-limiting examples of catalysts used in the present invention arerepresented by the structures:

When L¹ is a CAAC ligand and

and, X³ and X⁴ are independently S, and M is ruthenium then, the olefinmetathesis catalyst of Formula (2), is represented by the structure ofFormula (8A)

wherein: R¹, R², R^(a), R^(b) R^(3a), R^(3b), R^(4a), R^(4b) R⁵, R⁶, R⁷,R⁸ R⁹, R^(x), R^(y), R^(z), R^(w), X, Y, a and b are as defined herein.

The nomenclature of the structures of Formula (8A) is determined by theMoiety (A) structures selected from Table (4). For example, thestructure below is assigned Formula (8A10), since Moiety (A10) ispresent in the CAAC ligand.

TABLE 7 Olefin Metathesis Catalysts of Formula (8A)

Formula (8A5)

Formula (8A4)

Formula (8A1)

Formula (8A11)

Formula (8A2)

Formula (8A3)

Formula (8A8)

Formula (8A13)

Formula (8A12)

Formula (8A6)

Formula (8A7)

Formula (8A9)wherein: R¹, R^(1a), R^(1b), R², R^(a), R^(b) R^(3a), R^(3b), R^(4a),R^(4b) R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(z), R^(w), X, Y, a and b areas defined herein.

In other embodiments of the invention, the Group 8 metal olefinmetathesis catalysts of the invention are represented by the generalstructure of Formula (9)

wherein: M is a Group 8 transition metal; generally, M is ruthenium orosmium; typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1; typically, m is 0;

R^(aa) is unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(aa) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(aa) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(bb) is unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(b)b is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(b)b is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(aa) and R^(b)b can be linked to form a five-, six- or seven-memberedheterocycle ring with the nitrogen atom they are linked to;

R^(cc) is unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R is unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(cc) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(dd) is unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally R^(d) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically R^(d)d is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(cc) and R^(dd) can be linked to form a five-, six- or seven-memberedheterocycle ring with the nitrogen atom they are linked to;

R^(bb) and R^(cc) can be linked to form a five-, six- or seven-memberedheterocycle ring with the nitrogen atoms they are linked to;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically, X¹ and X² are independently chlorine, bromine, iodine orfluorine;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene.

In some embodiments of Formula (9),

is represented by

wherein: M, X¹, X², X³, X⁴, R^(x), R^(y), R^(w) and R^(z) are as definedherein.

In some embodiments of Formula (9), L¹ is

represented by

or by or L¹ is a CAAC ligand represented by

wherein Q¹, Q², p, q, R^(3a), R^(3b) R^(4a), R^(4b), R³, R⁴, R⁵ R⁶, R⁷,R⁸, R⁹, X⁵, Y⁵, a and b are as defined herein.

When M is Ru, n is 0, m is 0 and L¹ is a NHC ligand of structures

then the invention provides a catalyst represented by structures

and when

is represented by

then the invention provides a catalyst represented by structures

wherein R, R², R³, R⁴, R^(aa), R^(bb) R^(cc), R^(dd), X¹, X², X³, X⁴,R¹¹, R¹², R¹³, R¹⁴, R^(x), R^(y), R^(w) and R^(z) are as defined herein.

When M is Ru, n is 0, m is 0 and L is a CAAC ligand then the inventionprovides a catalyst represented by the structure of Formula (10A)

wherein: R¹, R², X¹, X², R^(3a), R^(3b), R^(4a), R^(4b), R^(aa), R^(bb),R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, X, Y, a and b are as defined herein.

The nomenclature of the structures of Formula (10A) is determined by theMoiety (A) structures selected from Table (4). For example, thestructure below is assigned Formula (10A10), since Moiety (A10) ispresent in the CAAC ligand.

TABLE 8 Olefin Metathesis Catalysts of Formula (10A)

Formula (10A5)

Formula (10A4)

Formula (10A1)

Formula (10A11)

Formula (10A2)

Formula (10A3)

Formula (10A8)

Formula (10A13)

Formula (10A12)

Formula (10A6)

Formula (10A7)

Formula (10A9)wherein: R¹, R^(1a), R^(1b), R², R^(a), R^(b) R^(3a), R^(3b), R^(4a),R^(4b), R^(aa), R^(bb), R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y),R^(z) R^(w), X, Y, a and b are as defined herein.

When M is Ru, n is 0, m is 0,

is represented by

X³ and X⁴ are S, and L¹ is a CAAC ligand then the invention provides acatalyst represented by the structure of Formula (12A)

wherein: R¹, R², R^(3a), R^(3b), R^(4a), R^(4b), R^(aa), R^(bb), R^(cc),R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(w), R^(z), X, Y, a and b areas defined herein.

The nomenclature of the structures of Formula (12A) is determined by theMoiety (A) structures selected from Table (4). For example, thestructure below is assigned Formula (12A5), since Moiety (A5) is presentin the CAAC ligand.

TABLE 9 Olefin Metathesis Catalysts of Formula (12A)

Formula (12A0)

Formula (12A4)

Formula (12A1)

Formula (12A11)

Formula (12A2)

Formula (12A3)

Formula (12A8)

Formula (12A13)

Formula (12A12)

Formula (12A6)

Formula (12A7)

Formula (12A9)wherein: R¹, R², R^(1a), R^(1b), R^(3a), R^(3b), R^(4a), R^(4b), R^(aa),R^(bb), R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(w), R^(z),X, Y, a and b are as defined herein.

Non-limiting examples of catalysts used in the present invention arerepresented by the structures:

Description of the Macrocyclic Embodiments

In one embodiment, the ring-close metathesis macrocyclic productcomprises a product internal olefin, wherein the product internal olefinis in a Z-configuration.

In some embodiments, the invention provides a method that produces acompound (i.e., a product, olefin product; e.g., ring-close metathesisproduct) having a carbon-carbon double bond (e.g., a product internalolefin) in a Z:E ratio greater than 95:5, greater than 96:4, greaterthan 97:3, greater than 98:2, or in some cases, greater than 99:1. Insome cases, about 100% of the carbon-carbon double bond produced in themetathesis reaction may have a Z configuration. The Z or cis selectivitymay also be expressed as a percentage of product formed (e.g.,ring-close metathesis product). In some cases, the product (e.g.,ring-close metathesis product) may be greater than 50% Z, greater than60% Z, greater than 70% Z, greater than 80% Z, greater than 90% Z,greater than 95% Z, greater than 96% Z, greater than 97% Z, greater thanabout 98% Z, greater than 99% Z, or in some cases greater than 99.5% Z.

In one embodiment, the ring-closing metathesis reaction product has acarbon-carbon double bond in a Z configuration and is represented by thestructure of Formula (A):

wherein:q is 1, 2, 3, or 4; andp is 4, 5, 6, or 7.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (A), wherein q is 2 and p is 4or 6.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (A), wherein q is 1, 2, 3 or 4and p is 6 or 7.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (A), wherein, q is 1 or 2 and pis 6.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (A), wherein q is 1, 2, 3 or 4and p is 7.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (A), wherein, q is 1 and p is 6.

In another embodiment, the ring-closing metathesis reaction product hasa carbon-carbon double bond in a Z configuration and is represented bythe structure of Formula (B):

wherein:r is 1, 2, 3, or 4; andv is 4, 5, 6, or 7.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (B), wherein r is 2 and v is 4or 6.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (B), wherein r is 1, 2, 3 or 4and v is 6 or 7.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (B), wherein, r is 1 or 2 and vis 6.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (B), wherein r is 1, 2, 3 or 4and v is 7.

In another embodiment, the at least one ring-close metathesis product isrepresented by the structure of Formula (B), wherein, r is 1 and v is 6.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (E):

wherein:R^(e) is H, methyl, ethyl, or propyl;q is 1, 2, 3, or 4;p is 4, 5, 6, or 7.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (E), wherein R^(e) is methyl, q is 2 and pis 4 or 6.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (E), wherein R^(e) is ethyl, q is 1, 2, 3or 4 and p is 6 or 7.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (E), wherein R^(e) is ethyl, q is 1 or 2and p is 6.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (E), wherein R^(e) is ethyl, q is 1, 2, 3or 4 and p is 7.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (E), wherein R^(e) is ethyl, q is 1 and pis 6.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one olefin metathesis catalyst of Formula (5), under conditionseffective to promote the formation of at least one Z-macrocycle productof Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one olefin metathesis catalyst of Formula (6), under conditionseffective to promote the formation of at least one Z-macrocycle productof Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one olefin metathesis catalyst of Formula (7), under conditionseffective to promote the formation of at least one Z-macrocycle productof Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (8),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (8A),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (9),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (10),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (10A),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (11),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (12),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In another embodiment, the invention relates to a method for performinga ring-closing metathesis reaction, comprising: contacting a dienestarting material bearing a Z-olefin moiety of Formula (E), with atleast one Z-stereoretentive olefin metathesis catalyst of Formula (12A),under conditions effective to promote the formation of at least oneZ-macrocycle product of Formula (A), with a Z-configuration greater than80% Z.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle, represented by Formula (A), comprising, a ring closingmetathesis reaction on a diene of Formula (E), in the presence of atleast one metathesis catalyst under conditions sufficient to form ametathesis product, wherein the at least one metathesis catalyst isrepresented by the structure of Formula (5), and wherein R^(e), q, p,R¹, R², R^(a), R^(b), X¹, X², R³ and R⁴ are as defined herein.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle, represented by Formula (A), comprising, a ring closingmetathesis reaction on a diene of Formula (E), in the presence of atleast one metathesis catalyst under conditions sufficient to form ametathesis product, wherein the at least one metathesis catalyst isrepresented by the structure of Formula (8), and wherein R^(e), q, p,R¹, R², R^(a), R^(b), R¹¹, R¹², R¹³, R¹⁴, R³, R⁴, R^(x), R^(y), R^(z)and R^(w) are as defined herein.

In one embodiment a Z-olefin moiety represented by Formula (E), whereinR^(e) is methyl, q is 2 and p is 4 or 6; is reacted in the presence of acatalyst represented by of Formula (8), wherein R¹ is hydrogen, R² isphenyl, ethyl or together with R¹ can form a phenylindenylidene, R^(a)is methyl, R^(b) is methyl, R¹¹ is hydrogen, R¹² is hydrogen, R¹³ ishydrogen, R¹⁴ is hydrogen, R³ is 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl,3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl or 2-methyl-phenyl, R^(x) is Cl, R^(y) is hydrogen,R^(z) is Cl and R^(w) is hydrogen, to give a musk macrocycle of Formula(A) with a Z-configuration greater than 80% Z.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle of Formula (A) comprising, performing a ring closingmetathesis reaction on a diene of Formula (E) wherein R^(e) is H,methyl, ethyl, or propyl; q is 1, 2, 3, or 4; p is 4, 5, 6, or 7; in thepresence of at least one metathesis catalyst under conditions sufficientto form a metathesis product, wherein the at least one metathesiscatalyst is represented by the structure of Formula (5), wherein thecatalyst is selected from: C591, C731, C625, C763, C663, C641, C647m,C747, C647, C676, C773, C673, C651 and C831m.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle of Formula (A) comprising, performing a ring closingmetathesis reaction on a diene of Formula (E) wherein R^(e) is H,methyl, ethyl, or propyl; q is 1, 2, 3, or 4; p is 4, 5, 6, or 7; in thepresence of at least one metathesis catalyst under conditions sufficientto form a metathesis product, wherein the at least one metathesiscatalyst is represented by the structure of Formula (8), wherein thecatalyst is selected from: C885ss, C785ss, C738ss, C869ss, and C725ss.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle of Formula (B) comprising, performing a ring closingmetathesis reaction on a diene of Formula (E) wherein R^(e) is H,methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7; in thepresence of at least one metathesis catalyst under conditions sufficientto form a metathesis product, wherein the at least one metathesiscatalyst is represented by the structure of Formula (12), wherein thecatalyst is selected from: C801_(TU), C701_(TU), C885_(TU), C881_(TU),C799_(TU), C951_(TU) and C799u_(TU).

In one embodiment, the invention provides for a method of synthesizingdilactones, such as ethylene brassylate (x=9) and ethyleneundecanedioate (x=7), both used in perfumery, wherein the startingmaterial can be obtained from a cross metathesis reaction in thepresence of at least one metal olefin metathesis catalyst of theinvention. The olefin is further reduced and cyclized using knownprocedures.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (F):

wherein:R^(f) is H, methyl, ethyl, or propyl;r is 1, 2, 3, or 4;v is 4, 5, 6, or 7.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (F), wherein R^(f) is methyl, r is 2 and vis 4 or 6.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (F), wherein R^(f) is ethyl, r is 1, 2, 3or 4 and v is 6 or 7.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (F), wherein R^(f) is ethyl, r is 1 or 2and v is 6.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (F), wherein R^(f) is ethyl, r is 1, 2, 3or 4 and v is 7.

In one embodiment, the diene starting material bearing a Z-olefin moietycan be represented by Formula (F), wherein R^(f) is ethyl, r is 1 and vis 6.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle of Formula (B) comprising, performing a ring closingmetathesis reaction on a diene of Formula (F) wherein R^(f) is H,methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7; in thepresence of at least one metathesis catalyst under conditions sufficientto form a metathesis product, wherein the at least one metathesiscatalyst is represented by the structure of Formula (5), wherein thecatalyst is selected from: C591, C731, C625, C763, C663, C641, C647m,C747, C647, C676, C773, C673, C651 and C831m.

In one embodiment, the invention provides for a method of synthesizing amusk macrocycle of Formula (B) comprising, performing a ring closingmetathesis reaction on a diene of Formula (F) wherein R^(f) is H,methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7; in thepresence of at least one metathesis catalyst under conditions sufficientto form a metathesis product, wherein the at least one metathesiscatalyst is represented by the structure of Formula (8), wherein thecatalyst is selected from: C885ss, C785ss, C738ss, C869ss, and C725ss.

In one embodiment the invention, provides for a method for synthesizinga musk macrocycle, represented by Formula (K)

the method comprising:a) contacting an olefin represented by Formula (G)

with at least one metathesis reaction partner represented by Formula (H)

in the presence of at least one olefin metathesis catalyst of Formula(4), Formula (5), Formula (6), or Formula (7), under conditionssufficient to form a metathesis product represented by the structure ofFormula (J):

wherein R^(1m) is H or methyl; OR^(2m) is a protected hydroxyl group,which may be selected from an alkyl ether group; an ester group; a silylether group; or a carbonate group; R^(3m) is branched or straight C₁-C₅alkyl; x is 2, 3, 4 or 5; and y is 5, 6, 7, or 8.

In one embodiment the invention, provides for a method for synthesizinga musk macrocycle, represented by Formula (K)

the method comprising:a) contacting an olefin represented by Formula (G)

with at least one metathesis reaction partner represented by Formula (H)

in the presence of at least one olefin metathesis catalyst of Formula(8), Formula (8A), Formula (9), Formula (10), Formula (10A), Formula(11), Formula (12), Formula (12A) or Formula (13) under conditionssufficient to form a metathesis product represented by the structure ofFormula (J):

wherein R^(1m) is H or methyl; OR^(2m) is a protected hydroxyl group,which may be selected from an alkyl ether group; an ester group; a silylether group; or a carbonate group; R^(3m) is branched or straight C₁-C₅alkyl; x is 2, 3, 4 or 5; and y is 5, 6, 7, or 8.

In one embodiment of the invention, one or both of first and secondolefins may be olefins with a terminal double bond.

In one embodiment of the invention one of the first or second olefin maybe represented by the Formula (G), wherein: R^(1m) is H or methyl;OR^(2m) is a protected hydroxyl group, which may be selected from analkyl ether group; an ester group; a silyl ether group; or a carbonategroup; and x is 2, 3, 4 or 5.

In one embodiment of the invention one of the first or second olefin maybe represented by the Formula (H), wherein: R^(3m) is branched orstraight C₁-C₅ alkyl; and y is 5, 6, 7, or 8.

In one embodiment of the invention, the intermediate formed during thecross-metathesis reaction between the first olefin of Formula (G), andthe second olefin, of Formula (H), in the presence of at least oneruthenium olefin metathesis catalyst, can be represented by the Formula(J), wherein: R^(1m) is H or methyl; OR^(2m) is a protected hydroxylgroup, which may be selected from an alkyl ether group, an ester group,a silyl ether group and a carbonate group; R^(3m) is branched orstraight C₁-C₅ alkyl; x is 2, 3, 4 or 5; R^(3m) is branched or straightC₁-C₅ alkyl; and y is 5, 6, 7, or 8.

TABLE 10 Musk Macrocycles name y x E/Z ambrettolide 7 6 7-ambrettolide 58 habanolide 9 3 9-hexadecen-16-olide 7 5

The intermediate of Formula (J) can be formed in the presence of any ofthe ruthenium metathesis catalysts represented by Formula (1), Formula(2), Formula (3), Formula (4), Formula (5), Formula (6), Formula (7),Formula (8), Formula (8A), Formula (9), Formula (10), Formula (10A),Formula (11), Formula (12), Formula (12A) or Formula (13). The rutheniumcatalyst can be selected from any of the structures defined, representedor exemplified herein.

Macrocyclic Products

Common macrocyclic musk compounds include ambrettolide (9-ambrettolideand 7-ambrettolide), nirvanolide, habanolide, cosmone, muscenone,velvione, civetone and globanone.

For example, the first and second olefin compounds that can be used toform 7-ambrettolide may be selected from 10-(tert-butoxy)dec-1-ene andmethyl oct-7-enoate or dec-9-en-1-yl acetate and methyl oct-7-enoate.The first and second olefin compounds that can be used to formHabanolide may be selected from trimethyl (pent-4-en-1-yloxy)silane andethyl dodec-11-enoate. The first and second olefin compounds that can beused to form Nirvanolide may be selected from4-methyl-6-(tert-butoxy)hex-1-ene and methyl 9-decenoate, or 4-methy1-6-(tert-butoxy)hex-1-ene and ethyl-9-decenoate, or3-methylhex-5-en-1-ylpropionate and methyl 9-decenoate.

As such, the method of the present invention, whereby a hetero-dimer isfirst formed by metathesis, and then ring-closed by a macrocyclizationstep, represents a considerably simpler and cheaper process than RCM toform macrocyclic musk compounds, which is industrially scalable in aneconomic manner.

As described above, a number of the macrocyclic derivatives obtained viathe methods of the invention can be used in the fragrance and flavorindustry. The macrocyclic derivatives include, for example, thecompounds listed in Table (11).

TABLE 11 Macrocyclic Products Name Structure (R)-(+)- Muscopyridine

(R)-(−)-Muscone

(Z)-oxacyclododec-8- en-2-one

Ethylene undecanedioate

Civetone

(E/Z)- oxacyclohexadec-11- en-2-one

(Z)-oxacyclotridec-10- en-2-one

(E/Z)- oxacycloheptadec-11- en-2-one

(Z)-oxacyclotetradec- 11-en-2-one

7-Ambrettolide

(Z)-oxacyclotetradec- 10-en-2-one

Habanolide

(Z)-oxacyclopentadec- 11-en-2-one

Nirvanolide

(Z)-oxacyclohexadec- 11-en-2-one

Cyclopentadecanolide (exaltolide)

(Z)-oxacycloheptadec- 11-en-2-one

Cyclopentadecanone (exaltone)

(E/Z)- oxacyclotetradec-10- en-2-one

Ethylene brassylate

(E/Z)- oxacyclopentadec-11- en-2-one

Cyclohexadecanone

EXPERIMENTAL General Information—Materials and Methods

Exemplary embodiments provided in accordance with the presentlydisclosed subject matter include, but are not limited to, the claims andthe following embodiments.

Unless otherwise specified, all manipulations were carried out underair-free conditions in dry glassware in a Vacuum Atmospheres Gloveboxfilled with N₂. General solvents were purified by passing throughsolvent purification columns. Commercially available substrates wereused as received. All solvents and substrates were sparged with Arbefore bringing into the glovebox and filtered over neutral alumina(Brockmann I) prior to use. The olefin metathesis catalysts used in thefollowing examples, were synthesized according to the proceduresdescribed in International Patent Applications PCT/US2017/046283 andPCT/US2018/027098.

Kinetic NMR experiments were performed on a Varian 600 MHz spectrometerwith an AutoX probe. Spectra were analyzed using MestReNova Ver. 8.1.2.¹H and ¹³C NMR characterization data were obtained on a Bruker 400 withProdigy broadband cryoprobe and referenced to residual protio-solvent.

All reactions involving metal complexes were conducted in oven-driedglassware under an argon or nitrogen atmosphere using standard Schlenktechniques. Chemicals and solvents were obtained from Sigma-Aldrich,Strem, Alfa Aesar, Nexeo, Brenntag, AG Layne and TCI. Commerciallyavailable reagents were used as received unless otherwise noted. Silicagel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

The following abbreviations are used in the examples:

mL milliliterL liter° C. degrees CelsiusCD₂Cl₂ deuterated dichloromethaneCDCl₃ deuterated chloroformC₆D₆ deuterated benzeneAr argonHCl hydrochloric acidKHMDS potassium bis(trimethylsilyl)amider.t. room temperatureTHF tetrahydrofuranNaHCO₃ sodium bicarbonateEt₂O diethyletherHCl hydrochloric acidMgSO₄ magnesium sulfateDCM dichloromethane

Example 1 Synthesis of C738ss

To a 20 mL scintillation vial equipped with a magnetic stir bar wasadded C747 (0.200 g, 0.268 mmol), dichloromethane (5 mL), and 3-hexene(0.066 mL, 0.536 mmol). The reaction was stirred for 30 minutes then(3,6-dichlorobenzene-1,2-dithiolato) (ethylenediamine)zinc(II) (0.099 g,0.295 mmol) and THF (5 mL) were added and the reaction stirred for anadditional 30 minutes before removing all volatiles in vacuo. Theresulting residue was extracted with dichloromethane (5 mL), passedthrough a syringe filter, then slowly combined with diethyl ether (30mL) to afford a brown microcrystalline solid. The solid was isolated byfiltration, washed with diethyl ether (1×10 mL) followed by hexanes(1×10 mL) then dried in vacuo to afford C738ss (0.132 g, 66.9% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 14.77 (dd, J=7.1, 3.6 Hz, 1H), 7.06 (d, J=8.2Hz, 1H), 7.05 (br s, 1H), 7.03 (br s, 1H), 6.96 (d, J=8.2 Hz, 1H), 6.92(br s, 1H), 6.83 (br s, 1H), 4.05-3.90 (m, 6H), 2.85 (s, 3H), 2.76 (s,3H), 2.58 (s, 3H), 2.53 (s, 3H), 2.28 (br s, 6H), 2.24 (s, 3H), 2.08 (s,3H), 0.35 (t, J=7.5 Hz, 3H).

Example 2 Synthesis of (Z)-4-Hexen-7-octenoate

To a 100 mL round-bottom flask charged with a stir bar were added 50 mLdichloromethane, 7-octenoic acid (1.54 mL, 10.0 mmol) and pyridine (80.7μL, 1.00 mmol). Oxalyl chloride (1.00 mL, 11.8 mmol) was added dropwise,and the reaction was stirred for overnight. Solvents were then removedin vacuum. 20 mL dichloromethane and pyridine (0.81 mL, 10.0 mmol) wereadded, and cis-4-hexenol (1.09 mL, 9.3 mmol) was subsequently addeddropwise at 0° C. After bringing the reaction to room temperature, itwas stirred for an additional 4 h. The reaction mixture was extractedwith 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layerwas dried over anhydrous MgSO₄, filtered, and solvents were removed invacuum. The product was purified by column chromatography on silica gel(5:95 Et₂O: pentane) to yield a colorless oil (1.58 g, 76% yield). The¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 3 Synthesis of (Z)-3-Hexenyl 9-decenoate

To a 100 mL round-bottom flask charged with a stir bar were added 50 mLdichloromethane, 9-decenoic acid (1.85 mL, 10.0 mmol) and pyridine (80.7μL, 1.00 mmol). Oxalyl chloride (1.00 mL, 11.8 mmol) was added dropwise,and the reaction was stirred for overnight. Solvents were then removedin vacuum. 20 mL dichloromethane and pyridine (0.81 mL, 10.0 mmol) wereadded, and cis-3-hexenol (1.10 mL, 9.3 mmol) was subsequently addeddropwise at 0° C. After bringing the reaction to room temperature, itwas stirred for an additional 4 h. The reaction mixture was extractedwith 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layerwas dried over anhydrous MgSO₄, filtered, and solvents were removed invacuum. The product was purified by column chromatography on silica gel(5:95 Et₂O: pentane) to yield a colorless oil (2.02 g, 86% yield). The¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 4 Synthesis of (Z)-3-Hexenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mLdichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine(0.89 mL, 11.0 mmol). Cis-3-hexenol (1.18 mL, 10.0 mmol) was then addeddropwise at 0° C. The reaction mixture was brought to room temperatureand stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl(200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried overanhydrous MgSO₄, filtered, and solvents were removed in vacuum. Theproduct was purified by column chromatography on silica gel (5:95 Et₂O:pentane) to yield a colorless oil (2.53 g, 95% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 5 Synthesis of (Z)-4-Hexenyl 9-decenoate

To a 100 mL round-bottom flask charged with a stir bar were added 50 mLdichloromethane, 9-decenoic acid (1.85 mL, 10.0 mmol) and pyridine (80.7μL, 1.00 mmol). Oxalyl chloride (1.00 mL, 11.8 mmol) was added dropwise,and the reaction was stirred for overnight. Solvents were then removedin vacuum. 20 mL dichloromethane and pyridine (0.81 mL, 10.0 mmol) wereadded, and cis-4-hexenol (1.09 mL, 9.3 mmol) was subsequently addeddropwise at 0° C. After bringing the reaction to room temperature, itwas stirred for an additional 4 h. The reaction mixture was extractedwith 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layerwas dried over anhydrous MgSO₄, filtered, and solvents were removed invacuum. The product was purified by column chromatography on silica gel(5:95 Et₂O: pentane) to yield a colorless oil (2.05 g, 87% yield). The HNMR and ¹³C NMR data correspond to the data found in the literature.

Example 6 Synthesis of (Z)-4-Hexenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mLdichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine(0.89 mL, 11.0 mmol). Cis-4-hexenol (1.17 mL, 10.0 mmol) was then addeddropwise at 0° C. The reaction mixture was brought to room temperatureand stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl(200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried overanhydrous MgSO₄, filtered, and solvents were removed in vacuum. Theproduct was purified by column chromatography on silica gel (5:95 Et₂O:pentane) to yield a colorless oil (2.45 g, 92% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 7 Synthesis of (Z)-5-Octenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mLdichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine(0.89 mL, 11.0 mmol). Cis-5-octenol (1.51 mL, 10.0 mmol) was then addeddropwise at 0° C.; the reaction mixture was brought to room temperatureand stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl(200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried overanhydrous MgSO₄, filtered, and solvents were removed in vacuum. Theproduct was purified by column chromatography on silica gel (5:95 Et₂O:pentane) to yield a colorless oil (2.82 g, 96% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 8 Synthesis (Z)-6-Nonenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mLdichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine(0.89 mL, 11.0 mmol). Cis-6-nonenol (1.67 mL, 10.0 mmol) was then addeddropwise at 0° C. The reaction mixture was brought to room temperatureand stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl(200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried overanhydrous MgSO₄, filtered, and solvents were removed in vacuum. Theproduct was purified by column chromatography on silica gel (5:95 Et₂O:pentane) to yield a colorless oil (2.74 g, 89% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 9 Synthesis of (Z)-Oxacyclododec-8-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added(Z)-4-hexenyl-7-octenoate (21.0 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C785ss (4.4 mg, 0.00563 mmol) in 1 mL DCM. The tube issealed and taken out of the glovebox. After one freeze, pump, thawcycle, the reaction flask is heated at 40° C. for 1 h and then quenchedwith 1 mL butyl vinyl ether. Solvents are removed in vacuum, and theproduct is purified by column chromatography on silica gel (1:49 Et₂O:pentane) to yield a colorless oil (12.0 mg, 70% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 10 Synthesis of (Z)-Oxacyclotridec-10-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added (Z)-3-hexenyl9-decenoate (23.7 mg, 0.0938 mmol) in 30.3 mL DCM and a solution ofC869ss (4.9 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and takenout of the glovebox. After one freeze, pump, thaw cycle, the reactionflask is heated at 40° C. for 1 h and then quenched with 1 mL butylvinyl ether. Solvents are removed in vacuum, and the product is purifiedby column chromatography on silica gel (1:49 Et₂O: pentane) to yield acolorless oil (12.5 mg, 68% yield). The ¹H NMR and ¹³C NMR datacorrespond to the data found in the literature.

Example 11 Synthesis of (Z)-Oxacyclotetradec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added (Z)-3-hexenyl10-undecenoate (25.0 mg, 0.0938 mmol) in 30.3 mL DCM and a solution ofC725ss (4.1 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and takenout of the glovebox. After one freeze, pump, thaw cycle, the reactionflask is heated at 40° C. for 1 h and then quenched with 1 mL butylvinyl ether. Solvents are removed in vacuum, and the product is purifiedby column chromatography on silica gel (1:49 Et₂O: pentane) to yield acolorless oil (13.2 mg, 67% yield). The ¹H NMR and ¹³C NMR datacorrespond to the data found in the literature.

Example 12 Synthesis of (Z)-Oxacyclotetradec-10-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-4-hexenyl 9-decenoate (23.7 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C738ss (4.2 mg, 0.00563 mmol) in 1 mL DCM. The tube issealed and taken out of the glovebox. After one freeze, pump, thawcycle, the reaction flask is heated at 40° C. for 1 h and then quenchedwith 1 mL butyl vinyl ether. Solvents are removed in vacuum, and theproduct is purified by column chromatography on silica gel (1:49 Et₂O:pentane) to yield a colorless oil (14.2 mg, 72% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 13 Synthesis of (Z)-Oxacyclopentadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-4-hexenyl 10-undecenoate (25.0 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C785ss (4.4 mg, 0.00563 mmol) in 1 mL DCM. The tube issealed and taken out of the glovebox. After one freeze, pump, thawcycle, the reaction flask is heated at 40° C. for 1 h and then quenchedwith 1 mL butyl vinyl ether. Solvents are removed in vacuum, and theproduct is purified by column chromatography on silica gel (1:49 Et₂O:pentane) to yield a colorless oil (15.6 mg, 70% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 14 Synthesis of (Z)-Oxacyclohexadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-5-octenyl 10-undecenoate (27.6 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C869ss (4.9 mg, 0.00563 mmol) in 1 mL DCM. The tube issealed and taken out of the glovebox. After one freeze, pump, thawcycle, the reaction flask is heated at 40° C. for 1 h and then quenchedwith 1 mL butyl vinyl ether. Solvents are removed in vacuum, and theproduct is purified by column chromatography on silica gel (1:49 Et₂O:pentane) to yield a colorless oil (17.7 mg, 79% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

Example 15 Synthesis of (Z)-Oxacycloheptadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-6-nonenyl 10-undecenoate (28.9 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C725ss (4.1 mg, 0.00563 mmol) in 1 mL DCM. The tube issealed and taken out of the glovebox. After one freeze, pump, thawcycle, the reaction flask is heated at 40° C. for 1 h and then quenchedwith 1 mL butyl vinyl ether. Solvents are removed in vacuum, and theproduct is purified by column chromatography on silica gel (1:49 Et₂O:pentane) to yield a colorless oil (17.8 mg, 75% yield). The ¹H NMR and¹³C NMR data correspond to the data found in the literature.

For determining selectivity, Z/E mixtures of lactones were synthesizedusing C647m as references for GC and ¹³C NMR studies for comparison. Themacrocyclic lactones synthesized herein are obtained in Z/E ratios from95/5 to 99/1.

Example 16 Synthesis of (E/Z)-Oxacyclotetradec-10-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-4-hexenyl 9-decenoate (23.7 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C647m (4.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealedand taken out of the glovebox. After one freeze, pump, thaw cycle, thereaction flask is heated at 40° C. for 4 h and then quenched with 1 mLbutyl vinyl ether. Solvents are removed in vacuum, and the product ispurified by column chromatography on silica gel (1:49 Et₂O: pentane) toyield a colorless oil (13.0 mg, 67% yield). The ¹H NMR and ¹³C NMR datacorrespond to the data found in the literature.

Example 17 Synthesis of (E/Z)-Oxacyclopentadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-4-hexenyl 10-undecenoate (25.0 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C647m (3.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealedand taken out of the glovebox. After one freeze, pump, thaw cycle, thereaction flask is heated at 40° C. for 4 h and then quenched with 1 mLbutyl vinyl ether. Solvents are removed in vacuum, and the product ispurified by column chromatography on silica gel (1:49 Et₂O: pentane) toyield a colorless oil (11.7 mg, 52% yield). The ¹H NMR and ¹³C NMR datacorrespond to the data found in the literature.

Example 18 Synthesis of (E/Z)-oxacyclohexadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-5-octenyl 10-undecenoate (27.6 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C647m (3.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealedand taken out of the glovebox. After one freeze, pump, thaw cycle, thereaction flask is heated at 40° C. for 4 h and then quenched with 1 mLbutyl vinyl ether. Solvents are removed in vacuum, and the product ispurified by column chromatography on silica gel (1:49 Et₂O: pentane) toyield a colorless oil (16.8 mg, 75% yield). The ¹H NMR and ¹³C NMR datacorrespond to the data found in the literature.

Example 19 Synthesis of (E/Z)-Oxacycloheptadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of(Z)-6-nonenyl 10-undecenoate (28.9 mg, 0.0938 mmol) in 30.3 mL DCM and asolution of C647m (3.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealedand taken out of the glovebox. After one freeze, pump, thaw cycle, thereaction flask is heated at 40° C. for 4 h and then quenched with 1 mLbutyl vinyl ether. Solvents are removed in vacuum, and the product ispurified by column chromatography on silica gel (1:49 Et₂O: pentane) toyield a colorless oil (16.4 mg. 69% yield). The ¹H NMR and ¹³C NMR datacorrespond to the data found in the literature.

1.-12. (canceled)
 13. (canceled)
 14. (canceled)
 15. An olefin metathesiscatalyst represented by the structure of Formula (5),

wherein: R¹ is hydrogen; R² is unsubstituted phenyl, substituted phenyl,C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked togetherto form an optionally substituted indenylidene; R^(a) is methyl, ethyl,n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; R^(b) is methyl,ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; or R^(a)and R^(b) are linked together to form a tetrahydrothiophene oxide withthe sulfoxide group; X¹ and X² are independently Cl, Br, F or I; R³ isadamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; andR⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl. 16.The olefin metathesis catalyst according to claim 15, selected from:


17. (canceled)
 18. An olefin metathesis catalyst represented by thestructure of Formula (8)

wherein: R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, cyclohexyl or phenyl; R^(b) is methyl, ethyl, n-propyl,iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) andR^(b) are linked together to form a five or a six-heterocyclic memberedring with the sulfoxide group; R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl,3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl or 2-methyl-phenyl; R¹ is hydrogen and R² isunsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted1-propenyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene; R¹¹ is hydrogen or methyl, R¹² is hydrogen ormethyl, R¹³ is hydrogen and R¹⁴ is hydrogen; R^(x) is methyl, hydrogenor Cl; R^(y) is hydrogen; R^(w) is hydrogen; R^(z) is Cl, t-butyl,hydrogen or phenyl; or R^(x) and R^(y) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(w) and R^(z) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(y) and R^(w) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl.
 19. The olefin metathesis catalyst according to claim18, selected from:


20. A method for synthesizing a musk macrocycle, represented by Formula(A):

comprising, performing a ring closing metathesis reaction on a diene ofFormula (E)

wherein: R^(e) is H, methyl, ethyl, or propyl; p is 1, 2, 3, or 4; q is4, 5, 6, or 7; in the presence of at least one metathesis catalyst underconditions sufficient to form a metathesis product, wherein the at leastone metathesis catalyst is represented by the structure of Formula (4):

wherein: M is a Group 8 transition metal; L² is a neutral electron donorligand; n is 0 or 1; m is 0, 1 or 2; R^(a) is hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; R^(b) is hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; or R^(a) and R^(b) arelinked together to form a five or a six-heterocyclic membered ring withthe sulfoxide group; X¹ and X² are independently anionic ligands; R¹ andR² are independently hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene; X⁵ and Y⁵ areindependently C, CR^(3A) or N; and only one of X⁵ or Y⁵ can be C orCR^(3A); R^(3A) is hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; Q is a two-atom linkagehaving the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or —[CR¹¹═CR¹³]—;R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; “s” and “t” are independently 1 or 2; R³ is unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; and R⁴ is unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl.
 21. The method accordingto claim 20, wherein the olefin metathesis catalyst is represented bythe structure of Formula (5),

wherein: R¹ is hydrogen; R² is unsubstituted phenyl, substituted phenyl,C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked togetherto form an optionally substituted indenylidene; R^(a) is methyl, ethyl,n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; R^(b) is methyl,ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; or R^(a)and R^(b) are linked together to form a tetrahydrothiophene oxide withthe sulfoxide group; X¹ and X² are independently Cl, Br, F or I; R³ isadamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; andR⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl. 22.The method according to claim 21, wherein the olefin metathesis catalystis selected from:


23. The method according to claim 20, wherein the olefin metathesiscatalyst is represented by the structure of Formula (8)

wherein: R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, cyclohexyl or phenyl; R^(b) is methyl, ethyl, n-propyl,iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) andR^(b) are linked together to form a five or a six-heterocyclic memberedring with the sulfoxide group; R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl,3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl or 2-methyl-phenyl; R¹ is hydrogen and R² isunsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted1-propenyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene; R¹¹ is hydrogen or methyl, R¹² is hydrogen ormethyl, R¹³ is hydrogen and R¹⁴ is hydrogen; R^(x) is methyl, hydrogenor Cl; R^(y) is hydrogen; R^(w) is hydrogen; R^(z) is Cl, t-butyl,hydrogen or phenyl; or R^(x) and R are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(w) and R^(z) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(y) and R^(w) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl.
 24. The method according to claim 23, wherein theolefin metathesis catalyst is selected from: